JPS5996150A - Highly filled halogen-containing resin composition - Google Patents

Abstract

PURPOSE:To provide the titled halogen-contg. resin compsn. having excellent stability and improved processability, by blending two specified kinds of organotin compds. in combination. CONSTITUTION:An alkyltin carboxylate of formula I [wherein R<1> is a 1-12C alkyl, aryl; R<2> is a 1-22C alkyl, alkoxyalkyl, alkenyl, aryl; m is 1, 2; k, l are each 1-3; k+l=4] such as monobutyltin tris(isooctyl thioglycolate) and an alkyltin maleate of formula II such as monobutyltin tris(butyl maleate) are used. 100pts.wt. halogen-contg. resin such as vinyl chloride resin, 50-700pts.wt. filler such as calcium carbonate or clay, 0.1-5pts.wt. alkyltin thiocarboxylate, and 0.01-5pts.wt. alkyltin maleate are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to highly filled halo r/containing resin compositions. More specifically, the present invention provides halogen-containing resin 10
In a composition containing 50 to 700 parts by weight of filler to 1 part by weight, the percentage sign is that an alkyltin thiocalnic acid ester salt and an alkyltin maleic acid ester salt are further added. , relates to a highly filler-containing halon-containing resin composition with improved processability and excellent stability.

Halogen-containing resins are subjected to various thermoforming processes depending on their intended use. At this time, coloration and physical deterioration occur due to the influence of heat. Until now, in order to prevent coloration and deterioration of this halogen-containing resin due to heat, Cd/Bα-based,
Stability rules are used for metal soaps such as B a / Z n series and Ca / Z n series, alkyl tin maleates, alkyl tin thiocal ester salts, and the like. However, especially in highly loaded rhodan-containing resins such as flooring materials, alkyl tin maleate exhibits a strong reddish color due to the influence of the filler, making it impossible to use them. Alkyltin thiocardates, which have been used for a long time, show relatively good coloring properties, but they are not strong enough, so zinc stearate, polyols, nitrogen compounds, etc. are added to improve the coloring properties. However, problems such as decreased thermal stability, excessive slipperiness, sublimation, and great out occur.

Furthermore, since highly filler-containing halogen-containing resins tend to stick, they are processed at low temperatures, which makes them difficult to wrap around calender rolls and glue in extruders. , tackifiers, processing aids, etc. are added, but they are not sufficient and the colorability is completely reduced.

Furthermore, the problem of deterioration of product surface properties due to inclusion of air bubbles has not yet been solved.

The inventors of the present invention have improved the processability of a highly filler-containing resin containing rodan by accelerating the winding property on a calender roll or the gluing property in an extruder, and preventing the inclusion of air bubbles on the product surface. In addition, in order to improve the initial coloring properties, it is effective to use alkyltin thiocargonate salts and alkyltin maleate salts in combination.To improve the processability of rhodan-containing resins for full gloss and highly filled side formulations. The method and stabilization method were successfully developed.

Thus, according to the present invention, No.Ro Jf7-containing resin 10
In a composition containing 50 to 700 parts by weight of filler to 0 parts by weight, (1) general formula % formula % alkyltin thiocarboxylic acid ester salt (R'' is carbon number 1
-12 alkyl group or aryl group, R2 alkyl group having 1 to 22 carbon atoms, alkoxyalkyl group, alkenyl group, cycloalkyl group, aralkyl group, aryl group, k = 1 to 3, m-1 to 2, l =i~3,k+1=j)
0.1 to 5 parts by weight, and (2) general formula (R') kS
n+0OCH=CHCOOR2) t (R117g2, k and l are as described above) 0.01 to 5 parts by weight are further added. A filling-side compounded logon-containing resin composition is provided.

The highly filler-containing halokene-containing resin composition of the present invention has a high rollability and quick gluing property in an extruder, making it easy to process and speeding up the process. The inclusion of air bubbles is extremely low, and the colorability is also significantly improved.

Above (11) alkyltin thioca kg
For example, monobutyltin tris (2-ethylhexylthioglycolate), monooctyltin tris (inoctylthioglycolate), monooctyltin tris (inoctylthioglycolate), etc.
, monooctyltin tris(2-ethylhexylthioglycolate), dibutyltin bis(inoctylthioglycolate), dibutyltin bis(2-ethylhexylthioglycolate), dibutyltin bis(inoctylthioglycolate) ), dibutyltin bis(2-ethylhexyl thioglycolate), dioctyltin bis(isooctyl glycolate), dibutyltin bis(methoxybutyl thioglycolate), dimethyltin bis(2-ethylhexyl Examples include ruthioglycoV--), ).

Examples of the alkyltin maleate salt represented by the general formula (2) include monobutyltin tris(methyl maleate), dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate), and subbutyltin. Examples thereof include bis(2-ethylhexyl maleate), butyltin bis(oleyl maleate), so-octyltin bis(butyl maleate), subbutyltin bis(cyclohexyl maleate), and subbutyltin bis(pentyl maleate).

The highly filler-containing halogen-containing resin composition of the present invention contains 50 to 70 parts of filler per 100 parts by weight of the halogen-containing resin.
Contains 0 parts by weight. If the filler is less than 50 parts by weight, the above-mentioned effect will not be observed even if the alkyl tin thiocarboxylic acid ester salt and the alkyl tin maleate salt are used in combination, and if the filler exceeds 700 parts by weight, processing will be difficult in practice. becomes. The preferred filler content is 100 to 500 parts by weight.

Conventionally, in halogen-containing resins that do not contain fillers,
In order to improve the weather resistance of alkyltin thiocarboxylic acid ester salts, which have excellent coloring properties, a part or all of the alkyltin thiocarboxylic acid ester salts have been replaced with alkyltin maleic ester salts. However, in this case, the use of alkyltin maleate salts has been associated with a decrease in coloring properties. In addition, since high-filler-containing halodan-containing resins are mainly used as interior flooring materials, weather resistance is not required. When added, it exhibits an intense reddish color due to the offsetting effect with the filler.
Furthermore, the addition of alkyltin maleate salts to highly filler-containing halodane-containing resins was unconventional, since processability such as roll wrapping properties deteriorated and air bubbles were mixed into the product surface. Therefore, as in the present invention, by using the alkyltin thiocarboxylic acid ester salt and the alkyltin maleic acid ester salt together in a highly filler-containing halodan-containing resin, the coloring properties of the alkyltin thiocarboxylic acid ester salt can be further improved, and the coloring property of the alkyltin thiocarboxylic acid ester salt can be further improved. It is surprising that we were able to speed up the rolling properties and the rolling process in the extruder, and to prevent air bubbles from entering the product surface.

The halogen-containing resins used in the present invention include vinyl chloride resin, vinylidene chloride resin, post-chlorinated vinyl chloride resin, chlorine-f polyethylene, and vinyl chloride and ethyl acrylate, acrylonitrile, styrene, maleic acid, vinyl acetate, Copolymers with inbutylene, ethylene vinyl acetate, etc., vinyl chloride resins and ABS resins, MBSj
Blended resin with resin, ethylene vinyl acetate resin, etc.
You can look up.

The fillers used in the present invention include calcium carbonate, clay, asbestos, silica, titanium, calcium silicate,
Antimony trioxide, magnesium carbonate, Merck, titanium oxide, etc. can be mentioned.

However, known stabilizers such as alkyl tin fatty acid salts, epoxidized soybean oil, epoxy resins, phosphites, antioxidants, diketones, nitrogen compounds, and sulfur compounds are added to the highly filler-blended halodan-containing resin of the present invention. , metal soaps, polyols, etc. may also be added. Further VC is a highly filler-blended halodane-containing resin of the present invention, a reactive plasticizer, a light stabilizer, a pigment, an antistatic agent, a great act inhibitor, a lubricant, a mold release agent, a 710 processing aid, a flame retardant, and a viscosity. Additives, foaming agents, adhesives, etc. may also be added. The highly filled halodan-containing resins of the present invention may also contain plasticizers, e.g.
Nooctyl phthalate, nohexyl phthalate, polyester plasticizers, etc. can be blended (plasticizers are essential components for flooring materials).

Next, the present invention will be explained in more detail with reference to all embodiments.

Example 1 and Comparative Example 1 The following formulation 't130'c was roll milled for 5 minutes using a roll to produce a uniform sheet lath with a thickness of 1 mm. At that time, what is the roll winding time? We also measured the presence of air bubbles on the sheet surface. Next, this sheet '1180
The gear set was placed in an aging tester at °C, and the coloration due to heat aging was measured. The results are shown in Table 1.

pvc (p=1ioo) io.

Ink Kagaku Kogyo) 10 Sooctyl phthalate 50 Calcium carbonate 100 Titanium oxide
.

Stabilizer See Table 1 Example 2
and Comparative Example 2 A test was conducted in the same manner as in Example 1 using the following formulation. The results are shown in Table 2.

Mixing (parts by weight)

Claims (1)

[Claims] 50 to 7 parts of filler per 100 parts by weight of halogen-containing resin
In a composition containing 00 parts by weight, (1) the general formula (
R' ) kS n (-S -IC-C)12+mC0
OR2, ], alkyltinthiocarboxylic acid ester mCR" is an alkyl group having 1 to 12 carbon atoms or an aryl group, R" (ti is an alkyl group having 1 to 22 carbon atoms, alkyl/alkyl group, alkenyl group, Cycloalkyl group, aralkyl group, aryl group, k=1~3, yn=1~
2, l=t~3, k11=4) 0.1~5 parts by weight, and (2) general formula (R'') kSn+0OCH=CHCO
OR2) Alkyl tin maleate salt represented by l (R1, R", k and l are as above) 0.01~
A highly filler-containing halo-containing resin composition, further comprising 5 parts by weight of additive.